Composite molding with adhesive composition layer comprising conjugated diene polymer having cyclic structure, and coating material

Abstract

A shaped composite article comprising a substrate and an adherend, which are comprised of different materials and are bonded together through a layer of an adhesive composition comprising as the main ingredient (i) a cyclic structure-containing conjugated diene polymer having a degree of cyclization of 30-95%, or (ii) a modified cyclic structure-containing conjugated diene polymer having a degree of cyclization of 30-95%, and having added thereto 0.1-20 wt. % of an α,β-ethylenically unsaturated carboxylic acid anhydride, wherein the ratio of {amount of (I) / [amount of (I)+amount of (II)]} is at least 60 wt. %, where (I) is an acid anhydride group added and (II) is a dicarboxylic acid group formed by hydrolysis of an acid anhydride group (I).

Description

TECHNICAL FIELD[0001]This invention relates to a shaped composite article comprising a substrate and an adherend, which are comprised of different materials, wherein the adherend is adhered onto the substrate through an adhesive composition layer comprising as the main ingredient a conjugated diene polymer having cyclic structures within the molecule. It further relates to a coating material comprising a conjugated diene polymer having cyclic structures within the molecule and having been modified with an anhydride of an α,β-ethylenically unsaturated carboxylic acid.BACKGROUND ART[0002]In many cases, adhesion of a substarte to an adherend comprised of a material different from the substrate is difficult.[0003]For example, a shaped article made of a hydrocarbon polymer, especially a polyolefin resin such as polypropylene or polyethylene, is used in combination with other different materials such as metals or fabrics for automobile parts, household appliances and construction material...

AI Technical Summary

Benefits of technology

[0049]The cyclic structure-containing conjugated diene polymer (i) and the modified cyclic structure-containing conjugated diene polymer (ii), used in the present invention, may be hydrogenated provided that the effect of the invention can be substantially obtained.

[0050]The procedure for hydrogenation is not particularly limited and can be conventional. Usually the cyclic structure-containing conjugated diene polymer (i) and the modified cyclic structure-containing conjugated diene polymer (ii) are contacted with hydrogen in the presence of a hydrogenation catalyst.

[0051]As the hydrogenation catalyst, those which are generally used for hydrogenation of olefin compounds can be used. The hydrogenation catalyst includes, for example, heterogeneous catalysts including a metal such as nickel, palladium or platinum, or including solid catalysts comprised of a metal such as nickel, palladium or platinum, supported on carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide; and homogeneous catalysts including those which contain a metal of group 8 of the periodic table.

[0052]The hydrogenation reaction can be carried out under appropriate conditions selected from a hydrogen pressure of 1 to 150 atmospheric pressures, and a temperature of 0 to 200° C., preferably 20 to 150° C.

[0053]The cyclic structure-containing conjugated diene polymer (i) and the modified cyclic structure-containing conjugated diene polymer (ii) preferably have a weight average molecular weight in the range of 5,000 to 600,000, more preferably 22,000 to 370,000 and especially preferably 37,000 to 230,000 as measured by gel permeation chromatography and as expressed in terms of that of standard polystyrene.

[0054]The adhesive composition used in the present invention can contain, in addition to the cyclic structure-containing conjugated diene polymer (i) and the modified cyclic structure-containing conjugated diene polymer (ii), additives which are widely incorporated in adhesives, according to the need. The additive includes, for example, a filler such as calcium carbonate and titanium oxide, a plasticizer, a surface active agent (leveling agent), an ultraviolet absorber, a light stabilizer, an antioxidant, a dehydrating agent, an adhesion-imparting agent, a pot life strengthener (such as acetylacetone, methanol and methyl orthoacetate) and an anti-cissing agent.

Problems solved by technology

In many cases, adhesion of a substarte to an adherend comprised of a material different from the substrate is difficult.

However, polyolefin resins such as polypropylene and polyethylene are non-polar and have a low solubility parameter (small sp value), and hence, are difficult to adhere to different materials such as metals, for example, iron and aluminum, and glass, ceramics, fabrics and polar polymers.

However, a high adhesion strength was difficult to obtain by this proposed method, and, the adhesion effect varies depending upon the material compositions of the particular combination of materials to be adhered, and the applicable adherend materials are limited.

However, in the case when the polyolefin shaped article to be adhered is made of a crystalline polyolefin resin such as polyethylene or polypropylene, the adhesion strength is still not high.

Further, in the case when the different material having a polar group to be adhered to the polyolefin shaped article has a relatively small sp value such as polyethylene terephthalate or polymethyl methacrylate, the adhesion strength is also not satisfactory.

Polyolefin rubbers such as an ethylene-non-conjugated diene copolymer (EPDM), and polyolefin resins such as polyethylene and polypropylene are non-polar and have a low solubility parameter (small sp value), and hence, these polyolefin rubbers and resins are difficult to adhere to a polar polymer having a large sp value.

Especially crystalline hydrocarbon polymers such as polypropylene and polyethylene have a high degree of crystallinity, and hence, are difficult to adhere to polyolefin elastomers and non-crystalline polyolefin resins even though these polyolefin elastomers and non-crystalline polyolefin resins have a sp value approximately equal to those of the crystalline hydrocarbon polymers.

However, even though these proposals are adopted, the adhesion strength is not sufficiently high and the kind of resin compositions to be adhered to a polyolefin rubber is limited.

This proposed method has a problem such that the adhesion strength is still not sufficiently high and the phenolic compound is not satisfactory from a viewpoint of environmental health.

However, the adhesion has not been improved to the desired extent, and hence, a further improvement is eagerly desired.

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